Metallizable triazine azo dyestuffs



Patented Dec. 18, 1945 2,391,164 7 7 g o METALLIZABLE TRIAZINEI AZODYESTUFFS Otto Kaiser, Basel, Switzerland, assignor to the firm ofSociety of Chemical Industry in Basle',

, Basel, Switzerland No Drawing. Application June/23, 1941'; Serial No.399,413. In Switzerland July 9, 1940 7 Claims. (01. 260-153) In the U.S. Patents No. 2,154,981 and 2,167,804 there are described inter aliagreen dyestufl's which have been obtained by uniting a blue element ofthe anthraquinone series, e. g., l-amino- 4- (4-aminophenyl)-aminoanthraquinone-2=sulionic acid" with yellow aminoazo dyestuffs, for

instance, with the aminoazo dyestuff which is formed 'bysaponificationof the product obtained by coupling diazotized acetyl-p-phenylenediamineand salicylic acid. The combination of the two dyestuff componentsoccurs advantageouslyby means of halides of polyvalent organic acids, oranalogues of such compounds, that is to say, compounds having halogenatoms capable of reacting, such as phosgene, the dichloride ofterephthalic acid, cyanuric chloride, cyanuricbromide,dichlorophenyltriazine, dichloroquinazoline, tribromopyrimidine, and thelike.

;These dyestuffs, if they contain the salicylicacid grouping, arecapable of forming complex copper salts. 'If' the formation of thecopper complexes is carried out on the fiber, for example, byaftertreatment of the dyeings with copper compounds, the wet fastness ofsuch dyeings is increased, but not in a sufiicient manner.

It has now been found that new dyestufis can be obtained if at least.one benzoylamino group be inserted between the yellow or blue componentsofthe dyestuffs of the patents mentioned in the first paragraph andtheconnecting link or atomic grouping which effects the union of these twoelements. These new dyestuffs differ from the green dyestuffs of theabove mentioned patents (which contain the atom groupingof salicylicacid in "theiryellow element) insofar as they yield dyeings, the wetfastness of which can be improved by aftertreatment with copper compounds to such an extent that quite generally they satisfy present dayrequirements; This'result is wholly surprising because it could not beanticipated that such a relatively small alteration of the constitutionwould be coupled with such an effect, particularly when the number ofthe positions in the dyestuff molecule capable of coupling with copperis not increased.

The new dyestufis therefore correspond with the general formula whereinthevarious'symbols-A, a, at, R1-N=N-R2 have the following signification:A=the radical of, a blue aminoanthraquinone dyestufi; one z=a connectinglink selected from the group consisting of V H O.

group whichis linkedwiththe connecting member at,v and the other 1 for ahydrogen atom); the other z=an 1/ group (the two ys also having themeaning given: above); m=a connecting link. selected from the groupconsisting of II II II' A II H O S O 1 O O and the radical of aheterocyclic six-membered system, whose heterocyclic six-membered ringconsists of carbon ,and nitrogen atoms of which at least 3 and not morethan 4 are carbon atoms, and at least 2' and not more than 3. arenitrogen atoms, not more than 2 nitrogen atoms being linked with eachother, which heterocyclic sixmembered ring, contains at least twice andnot more than three times the atom grouping R1-N=N-R2=radica1 of ayellow azo dyestufi wherein R1 stands for an aromatic ring of thebenzene series, in which ring the group of the symbol a and the azogroup stand in a position to each other which is different from theo-position, and wherein R2 stands for a radical which causes the yellowcolor of the atom grouping R1-N=N-R2 and is characterized by a benzenering in which an OH- and a COOI-I- group stand in o-position to eachother.

Particularly valuable are the dyestuffs in which the. radical A standsfor the radical of a blue aminoaryl-aminoanthraquinone dyestufi. In thiscase the new dyestuffs correspond to the general formula wherein a, a:and R1 -N '=NRz have the mean ings already mentioned, and wherein r thenstands for the aminoanthraduinone radical of a, blue aminoanthraquinonedyestuff, and

stands for the radical of a monoor binuclear aromatic amine.

Of particular value are the dyestufis in which the symbol 1'1 stands forthe radical of a 1:4--diamino-anthraquinone-Z-sulfonic acid, and inwhich the other symbols Rs, 2, a: and R1--N=N-R2 have the meaningsindicated above.

In such dyestuils R3 may, for instance, correspond to the followingaromatic monoto binuclear diamines: 1:4-diaminobenzene,1:3-cliaminobenzene, 1:4-diaminobenzene-3-sulfonic acid, 13-diaminobenzene-4 -sulfonic acid, 4 4'-diaminodiphenyl,4:4'-diamino-3:3'-dimethylor -dimethoxydiphenyl, 44'-diaminodiphenyl-3-sulionic acid, 4:4-diaminostilbene,4:4'-diaminodiphenylmethane, 4:4 diaminodiphenylurea, 4:4'-diaminobenzoy1aniline, 3 3-diaminobenzoylaniline, 4 3'-diaminobenzoylaniline, 4 4'-diaminodiphenylurea-3'-sulfonic acid,4:4-diaminodiphenyl-Z-sulfonic acid.

Further the atom grouping R1N=NR2 may be derived from the followingaminoazo dyestufis: Lamina-4' hydroxy 1:1'-azobenzene 3'- carboxylicacid, 3-amino-4'-hydroxy-l:1-azobenzene-3'-carboxylic acid,4-amino-4'-hydroxyl 1 '-azobenzene-3-sulfo-3-carboxylic acid, 4-amino-4'-hydroxy-1: l'-azobenzene 5'-sulfo-3'- carboxylic acid,4-amino-2-methyl-4'-hydroxy- 1:1-azobenzene-3-carboxylic acid,4-amino-2- methyl-4'-hydroxy-1: l '-azobenzene-5'-sulfo -3- carboxylicacid, 4-amino-3-methyl-4-hydroxylz1-azobenzene-5'-sulfo-3'-carboxylicacid, 4- amino-3-methoxy 6 methyl4-hydroxy-1:lazobenzene-5'-sulfo-3'-carboxylic acid. It may also bederived from somewhat more complicated aminoazo dyestuffs, such as, forexample, the saponification product of the azo dyestuff from diazotized4-acetylaminoor 3-acetylamino-1- aminobenzene and1-(4-hydroxy-3'-carboxy)- phenyl-3-methy1-5-pyrazolone, etc.

The atom groupings i f Br-O O-Br tribromomethylpyrimidine of the formulaN 0 C--Br dichloroquinazoline of the formula dichlorophthalazine of theformula (etc) Of particular importance, however, are the connectinglinks which are derived from triazine derivatives, both on account ofthe good properties of the final dyestuffs obtained therefrom, and alsobecause of the easy accessibility of such. products and their goodreactability.

Among the blue aminoanthraquinone dyestuffs there come intoconsideration inter alia polyaminoanthraquinones, such as, for example,1:4:5:8-tetraaminoanthraquinone, 1:4:5 triamino-8-hydroxyanthraquinoneor 1:5-diamino- 4:8-dihydroxyanthraquinone, further l-amino-4-aminoarylidoanthraquinones, particularly the sulfonic acids of suchproducts. Of particular value for the production of the dyestufis hereunder consideration are the l-aminol-aminoarylidoanthraquinones of thegeneral formula a l H H wherein i -N--R-NH| stands for the radical of amonoto binuclear aromatic diamine, and K for an alkyl radical or for ahydrogen atom.

From the above statements it follows, therefore, that among thedyestuffs of the present application those are of especial interestwhich in their free state correspond to the general formula wherein K,R3, 2 and R1N=NRz have the already indicated signification, and R4stands for a monovalent substituent which may, for instance, consist ofahalogen atom, an OH group, an NH2- group, an alkyl group, or an arylradical. But particularly valuable are the dyestuffs whereincorrespondstothe'radical of a; pr isulfo] anilidoanthraquinone 2sulfonic acidmew-or: secondaryamine; that is to say to: the are added asaneutral solution in 1000 partsof symbol water to; a suspension of 185parts of cyanuric I I chloride in 500 parts of cold water. The tern- 1 5perature. is kept at 101to C.- for one hour. The

" M hydrochloric acid formed during the condensa- I I Y t r 7 tion isneutralized by a corresponding quantity 01 wherein ostan'dsfor ahydrogen atoin or an alkyl; sodium carbonate. 25.7 parts of4-amino-4'-hyradical, and t for an alkyl radical or anaryl raddroXY- '-an -3'- r y1 a id dismal; i l0 solved in500 parts of warm water are thenadded to them'ono-condensation product. The temperv v ature is therebyraised to 40? C'. After two hours g 18 parts of aniline are added andthe temperi ature kept at 80 C. for an equal-period, when the may, forinstance, correspond to the radicals of H5 formation of the tertiarycondensation product is the followingamines:mono-methylamine,monccomplete. his separated with sodium chlorideethylamine, diethylamine, n-mono-butylamine, and dried. The productcorresponding in the aniline, 'p-toluidin e, p-an inosalicylic acid, 5-freestate to the probable formula v 'N=N k on COOH naphthylamine, Inaphthylamino 6 sulfonic dyes cotton from a weakly alkaline bath in theacid, 4-amino-4"-hydroxy'-1 :1'-azobenzene-3- resence of copper sulfateand tartrate of sodium carboxylic acid, 4-amino-4-benZoylamino-1-hygreentintswhich are fast to washing and to light. droxybenzene-2-carboxylicacid. etc. If theaniline used in the above example be re- The-iollowingexamples illustrate theinvenplaced by a Second 25.7 parts of 4-amino-4-tion, the parts beingby-weight: HY IOXY- :1-azobenZene -3-carboxy1icacid, a 1 product is obtained which dyes cotton in yellow- 0 ExamplQlis'h green tints. The product, in the free state,

48.9- parts of 1-amino-4-(4"-amino-3'-su1fo) corresponds to the robableformula anilido-anthraquinone-2-sulfonic acid are dis I f parts of themonoazo dyestuff obtained by Solved as disodium y; in 50 partS of wateruniting molecular proportions of diazotized 1- f s d'um bicarbonate. y mxybenzene 5 sulfonic with addmon of parts 0 1 acid and 1-methyl-3-amino-4-methoxybenzene,

T solutloans t e -F'P Wlth followed by treatment of the formed monoazoparts of 4-mtrob Whlch been dyestufiwith 4-nitrobenzoylchloride andsubsemixed with 10 parts of acetone. The mtrobenfluent reduction be usedinstead of l parts of zoyl product formed is reduced to the correspond-4-amino-4'-hydroxy 1 1' azobenzene 3'-ca,ring aminobenzoyl products at-70 c. with 42 boxylic ci i e production of the dy tuff of v the firstparagraph of this Example there is 1 n partsvof crystallized SodiumSulfide dlsso Ved 1 obtained a product which dyes cotton yellowish f hifi p w green tints having the same fastness properties. reduct n P O abe deslsnated This d, estufi inthe free state, very probably cor- SOsHExample 2 i I zene-3'-carboxylic acid instead of aniline there; is

2537 parts of r x obtained a dyestuff which dyes cotton inyellowzene-3'carboxylic acid are dissolved as sodium i green tintshaving the s f s p ope salt in 250 arts of water with addition f 3,4ties. It corresponds in the free state to the probparts of sodiumbicarbonate. This solution is able formula r sons OH N=N NHCO NHC o 1 iN NH NH coon treated at about 60 C. with 18.5 parts of 3-nitro- 20Example 3 benzoylchloride which have been mixed with 10 parts of acetoneand kept at the temperature of iii fifggg g g metlgl 4 g 80 C. for onehour. The nitrobenzoyl product is -c r 9 y in am are 1550 reduced at 60C with 42 parts'of crystallized sodium Salt m 50 palts of Water Wlthsodium sulfide, dissolved in 100 parts of water, to 233. 12 22222 zg g gg g the corresponding aminobenzoyl product. 25 W1 par S 37.6 parts ofthe separated reduction product" 'm-ilgfienzos-dchlomde whlch have beenImxed are added as a neutral solution in 1000 parts of 22 h g gg 1s keptail-8O for Water to a suspension of 18.5 parts of cyanuric o e m m nzoypro-duct 1S .reduced chloride in 500 parts of cold water The temperat 60with l parts of crystalhzed Sodmm ature is kept at to 10 C for tv'vohours The 3D fide, dissolved n 1000 parts of water, to thecorhydrochloric acid formed during the conde s gsi t s oifi l i z ei aigtt 122 31225011 r d t tion is neutralized by a corresponding quantity ofadded as a neutr 1 1000 p o W sodium carbonate. A neutral solution of489 a so u Ion m pangs of wapel to a suspension of 18.5 parts ofcyanuric chloride parts of l-amino-i-(4'-amino-3'-sulfo)-anllidoin 500 tanthraquinone-Q-sulfonic acid in 1000 parts of kept 3 02: ggi gg fi g fggfiiggggg gz Water iS then added to the mono'condensation acid formedduring the condensation is neuprod c a the f f f 1S mlsed to C; tralizedby a corresponding quantity of sodium ThlS temperature is maintained for20 hours, and carbonate A neutral solution f'60 parts of thehydrochloric acid which has been liberated is 40 amino 4 [4' (4"aminobenz y1) 3 neutralized little by ttl with the correspondingsulfo]-anilidoanthraquinone-Z-sulfonic acidcf.

quantity of sodium, carbonate. 18 parts of ani- Example 1000 I parts ofwater is then added lme are then added and the t pe 15 kept to themono-condensation product and the temat 80-85 C. for 3 hours. The W o ismade perature is raised to 40 C. This temperature is tinctly alkalinewith sodium carbonate; the trimaintained for 20 hours and t hydrochloricco de a P t formed is separated with .acid which has been liberated isneutralized litsodium chloride and dried. tle by little with thecorresponding quantity of The product in the free state corresponds verysodium carbonate. Then, 15.3 parts of 4-aminoprobably to the formulasalicylic acid are added and the temperature is N/ N SIOaH coon and dyescotton from a weakly alkaline bath in so kept at lo-85 C. for threehours. The whole is the presence of copper sulfate and tartrate of madedistinctly alkaline with sodium carbonate,

sodium green tints which are fast to washing and the tri-condensationproduct is separated with to light. sodium chloride and dried.

If in the above example use is made of a second Th product,corresponding in the free state 25.7 parts of4-amino-4'-hydroxy-1:1-azobento the probable formula dyes cotton from aweakly alkaline bath in the presence of copper sulfate and tartrate ofsodium green tints which are fast to washing and to light.

Example 4 be detected after this time the condensation productformed isfiltered, if necessary. after addition of sodium chloride. It isdissolved in water as sodium salt and precipitatedwith sodium chlorideand dried.

. The product, corresponding in the to the, probable formula free stateI O NHQNHCOO-NH 80.11 L 0.0... QeHOO NJ.

COOH dyes cotton from a weakly alkaline bath in the presence of coppersulfate and tartrate of sodium green tints which are fast to washing andto light.

When proceeding in an analogous manner with the other combinations,mentioned in the remaining examples, similar dyestufis are obtained.

Example H 25:1 parts of 4-amino-4'-hydroxy-1:1-azobenzene-3-carboxylicacid are dissolved as sodium of sodium bicarbonate. at about 60 C. with18.5 parts of 3-nitrobenzoylchloride which have been mixed with 10 partsof acetone and kept at the temperature of 80 C. for one hour. Thenitrobenzoyl product is reduced at 60 C. with 42 parts of crystallizedsodium sulfide, dissolved in 100 parts of water, to the correspondingaminobenzoyl product.

s Q Q 37.6 parts of the separated reduction product Q perature isjkeptat 5-10 C." for two hours. The hydrochloric acid formed during thecondensation is neutralized by a corresponding quantity of sodiumcarbonate. A neutral solution of 43 parts of1.5-dioxy-4.8-diaminoanthraquinone 2.6- disulfonic acid dissolved in1000 parts of water is then added, to the mono-condensation product. Thetemperature is raised to 40 C. This temperature is'maintained for 2hours and the hydrochloric acid which has beenliberated is neutralizedlittle by little with the corresponding quantity of sodium carbonate. 18parts of aniline are then added and the temperature is kept at C. forthree hours. The'whole is made distinctlyalkaline with sodium carbonate;the tricondensation product formed is separated with sodium chloride anddried.

The product dyes cotton from a weakly alkaline bath in the presence ofcopper sulfate and tartrate of sodium green tints which are fast towashing and to light. It corresponds in the free state to the probableformula Example 6 1 parts of water, to the corresponding aminobenzoylproduct.

60.8 parts of the separated reduction product are dissolved as sodiumsalt in 1000 parts of water, a solution of 16.3 parts of4-methyl-2.6-dichloropyrimidine in. 400 parts of acetone is added andthe mixture isheated at 50-60 C. for 4 hours with thorough stirring in avessel connected with a descending condenser. The hydrochloric acidformed duringthe condensation is neutralized by a corresponding quantityof sodium carbonate. A neutral solution of 25.7 parts of4-amino-4-hydroxy-l:l'-azobenzene-3'-carboxylic acid in 1000 salt in 250parts of water with addition Ora/l parts 1 Parts Water is then added tothe mono-conden- This solution is treated 'sation product and thetemperature is raised to 90-95 C. This temperature is maintained for 4hours, and the hydrochloric acid which has been liberated is neutralizedlittle by little with the corresponding quantity of sodium carbonate.

The whole is made distinctly alkaline with sodium carbonate; thedi-condensation product formed is separated with sodium chloride anddried. I

The product dyes cotton from a weakly alkaline bath in the presence ofcopper sulfate and tartrate of sodium green tints which are fastto'washing'and to light. It correspondslvery probably to the formulacoon Ilecular proportion of por m-pheny1ene'-di-.

amine, 1 mol m-phenylenediaminesulfonic acid, 1 mol 4:4'diaminodiphenyl,1 mol 4 4-diamin0- diphenyl-3-sulfonic acid, 1 mol4;4',-diaminostilbene, 1 mol 4:4-diaminodiphenylmethane,'1 mol4:4-diamino-diphenylurea-S'-sulf0nic acid etc., work is carried out in asimilar manner.

In the above examples the yellow aminoazo dyestufis may also be replacedby further similarly constituted dyestuffs such as: 4-amino-2- methyl-4-hydroxy- 1:1 -azobenzene-3' -carbdxyl-' ic acid,,4-amino-2-methyl-4'-hydroxy-1:1'-azobenzene 5" 7 sulfo 3' carboxylicacid, 4 (4'5- aminobenzoyl) amino 2 methyl-4f-hydroxy- 1:1 azobenzene 5sulfo 3 carboxylic acid, 4 (3" aminobenzoyl) amino 2 methyl 4-hydroxy-l:1-azobenzene-5' sulfo-3-carboxylic acid, 4 amino -2.5 dimethyl-4'- hydroxy-1:1'- azobenzene-3'-carboxylic acid.

There come also into consideration products such as the azo dyestufiwhich is obtained by HO N uniting diazotized p' -aminosalicylic acidwith pyrazolones of the formula 7 CH; V V I V V H .SOtH SOgH O or (IE3C= -N and derivatives thereof which are obtained by 30 acylating theamino group with compounds such 35 made in theprocedure according to theproperties of the 1 intermediate products employed. These alterationsare obvious to anyone skilled in the art. Such dyestuffs are forinstance /N\ at if"? WO O O H l H H s H on, 00011 a N-H memes p 7 H i lt Oi-R O Q O NH:

' /N\ l '7 III 1 -fi- I -III(I3/ iiN- -(i-E N=N on H N a I I H H soda: Ip H: oooH H a /N e H I 80m K/ 0011 4}) from the vsulfonation product of;7 of crystallized sodium sulfate added, and the material is dyed at thistemperatur for hour.

if v 2 parts of a solution of crystallized copper sulfate neutralizedwith caustic soda solution and 2.5 parts of tartaric acid in 100 partsof water are then added to the dyebath and the cotton is treated forhour at about C. in this a 5 bath. The material is then rinsed as usualand 0-0- dried. It is dyed in fast, pure green tints.

The dye'stufis of the present application may Example 7 also be used onunion goods such as, for example, wool-viscose staple fiber mixture. Insuch parts of cotton are entered into a dyebath 7.0 cases. dyeing isconducted advantageously in a contalhing-3000 parts of water atJ40-50C., 1.5 neutral bath in the presence of sodium or potasparts of thedyestufi prepared according to the sium chromate. first paragraph ofExample 1, and 2 parts of What I claim is: anhydrous sodium carbonate.The bath is then i. The dyestuffs which at the same time belong heatedwithm' /g hour tom-9 C- nd 30 P r I? to the anthraquinone series and-tothe azo series and correspond in the free state to the formula standsfor the radical of a diamine selected from the group consisting of a1:4-phenylenediamine, a 4:4-diaminodiphenyl and a,4:4'-diaminodiphenylurea; one 2 stands for a connecting link consistingof a group, wherein one :1] stands for a hydrogen atom and the other :1stands for an group linked to an atom grouping of the connecting memberso; :2: stands for a 1,3,5-

triazine nucleus having attached to the 4-carbon atom an groupingwherein o is a member of the group consisting of hydrogen and loweralkyi, and t is a member of the group consisting of lower alkyl andaryl; and the other 2 stands for a member of the group consisting of theaforesaid connecting link and a single bond; and wherein finally thesymbols l;T-R;-N=NR1 stand for the radical of ayellow aminoazo dyestuffin which'R1 represents an aromatic ring of the benzene series in whichring the group of the symbol a and the azo group stand in para positionto each other, and R2 represents a benzene ring in which an OH group anda COOH group stand in o-position to each other and in which the OH--group stands in p-posi- .tion to the N=N- group, which dyestufis yieldgreen tints on vegetable fibers whose wet fastness may be enhanced bytreatment with cop P Iii mpQundSJt.i.,.,,l.1'.i A" i 2. The dyestuffswhich at the same time belong to the anthraquinone series and to the azoseries and correspond in the free 'state to the general formula standsfor the radical of a diamine selected from the group consisting of a1:4-phenylene-diamine, a 4:4'-diamino'dipheny1 and a4:4'-diaminodiphenylurea, one 2 stands for a connecting link consistingof a g group-in which group one 1! stands for an group linked to acarbon atom of the triazine nucleus and the other 1/ for a hydrogenatomand the other .2 stands for a member of the group consisting of thesame connecting link and a single bond, and wherein finally the symbolsstand for the radical of a yellow aminoa'z odye-l stuff in which R1means an aromatic ring of the benzene series in which ringthe stands forthe radical of a diamine selected from the group consisting of a1:4-phenylene-diamine, a 4:4'-diaminodiphenyl and a4:4'-diaminodiphenylureaqone z stands,fora\ group in whichlatter groupone :1 stands fcqr an group linked to a carbon atom of the triazinenucleus and the other y stands for a hydrogen atom, and the other 2stands for a single bond, and wherein finally the symbols stand for theradical of a yellow aminoazo dyestuff in which R1 means an aromatic ringof the benzene series in which ring the group and the azo group stand inpara position to each other, and R2 means a benzene ring in which an OH-group and a COOH group stand in o-position to each other and the OI-L-group stands in para position to the N=N- group, which dyestufis yieldgreen tints on Vegetable fiber whose wet fastness may be enhanced bytreatmentwith copper compounds.

CODE

4. The dyestufis which at the same time belong to the anthraquinoneseries and to the azo series SOsH Y I l H N 1% (III) A I OH:

mdWQ eSm fim-thefreesstatet the nmfl H-N-lower alkyl whereimone 2 standsfor a group linked to a carbon atom of the t'riazine nucleus and theother y stands for a hydrogen atom-, and the other 2 stands for a singlebond,

and wherein finally the symbols NR,N=NR

stand for the radical of a yellow aminoazo dyestuff in which R1 means anaromatic ring of the benzene series in which ring the group of thesymbol a and the azo grou stand in 1:4-position to each other, and R2means a henzene ring in which an OH- group and a COOH group stand ino-position to each other and in which the OI-I- group stands inp-position to the -N=N- group, which dyestuffs yield green tints onvegetable fiber whose wet fastness may be enhanced bytreatment withcopper compounds.

5. The dyestufi corresponding in the free state i to the formula 00 OHSIOaH 6. The dyestuff corresponding in the free state to the formulaCOOH l HN-CHa 7. The dyestufi'corrsponding m the free "stat' to theformula 7 0 R G F-H w 0/ G .H H i) H H BIT 1% 0B. 00011 o'r ro KAISER.

